Preparationand Properties Of Novel Fluorosilicone Surfactants

Silicone surfactants have many excellent properties, such as low surface tension, good emulsifying, wetting, lubricating and so on. But Silicone surfactants have a disadvantage, which is poor chemical resistance. Adding the organic fluorine into the polysiloxane, the novel fluorosilicone surfactants can be obtained, which shows lower surface tension, chemical stability, and etc. They are widely used in aerospace, automotive, textile and other fields. This paper aims to synthesize three different ionic types of novel fluorine silicone surfactants by solution polymerization, which have high surface activity and can effectively improve the fabric softness, decontamination and oil resistance when used in fabric finishing, and which have little effect on the whiteness and hygroscopicity of the finished fabrics. Therefore, the main research contents of this paper are as follows:Three different ionic types of novel fluorosilicone surfactants were synthesized by solution polymerization. The initial intermediate hydrogen-conta-ining fluorinated silicone (FPHMS) was prepared by the acid-catalyzed ring-opening polymerization reaction, using 1,3,5-trimethyl-1,3,5-tri(3’,3’, 3’-trifluoropropyl) cyclotrisiloxane (D3F), octamethylcyclotetrasiloxane(D4), tetramethylcyclotetrasiloxane(D4H), hexamethyldisiloxane(MM) as the raw materials. Then epoxy-terminated polyether-modified fluorine silicone polymer (EPFS) and terminal hydroxyl polyether-modified fluorine silicone polymer (PFS) of the further intermediates were synthesized by hydrosilylation reaction with FPHMS, epoxy-terminated allyl polyether, and ally 1 polyether. Then, QAFS was prepared with EPFS and tertiary amine by ammonolysis ring-opening reaction. AFSS was also synthesized with EPFS, diethylamine and chloroacetic acid by ammonolysis ring-opening reaction. CFSS was prepared by esterification reaction with PFS and maleic anhydride. The structures of the products were characterized by IR and 1H NMR, confirming the product as target substances. And the optimum synthesis processes of products were discussed by the orthogonal design. The experiments showed that the best synthesis process of QAFS is as follows:the reaction temperature is 80～85℃, the reaction time is 6h and the material ratio of n(EPFS):n(TEA) is 1:1.05. The best synthesis process of AFSS is as follows:the material ratio of n(EPFS):n(diethylamine) is 1:1, n(diethylamide):n(chloroacetic acid) is 1:1.2, the reaction time is 6h and the reaction temperature is 80℃. The best synthesis process of CFSS is as follows: material ratio of n(PFS):n(maleic anhydride) is 1:1.1, the reaction time is 8h, the reaction temperature is 70℃Through the research on the basic physical and chemical properties of QAFS, AFSS and CFSS, the relationship between the ion types of the products and surface properties was obtained. The measurement results on the critical micelle concentration (cmc) and surface tension (γcmc) showed that quaternary ammonium salt cationic surfactant has more excellent interfacial properties than that of the anionic and amphoteric fluorosilicone surfactants. Its critical micelle concentration is 0.275g/L and surface tension (γcmc) reached 20.21mN/m. It was found in solubilizing power of benzene research that the solubilizing power of benzene of QAFS is stronger than that of AFSS and CFSS, and it is up to 3.0. It was found in emulsifying capacity research that QAFS has a larger capacity of emulsifying capacity and reaches 1590s. The emulsifying power of CFSS and AFSS in benzene is up to 200s,530s. It was found in stability of surfactants research that three different ionic types of fluorosilicone surfactants are extremely stable in the environment of acid and alkali salt. The stability in hard water is also very good. The average stability and differential stability of them all reache five.The softness, oil resistance, decontamination and other performance of QAFS/Fab, AFSS/Fab, CFSS/Fab, which finished by QAFS, AFSS, CFSS in the fabric finishing, have been significantly improved. And the best process conditions of QAFS is as follows:finishing solution concentration is 0.4 g (100mL water)-1, the setting temperature is 150℃, the setting time is 60s. Under the optimum fabric finishing process, the softness of the finished fabrics is improved significantly. Especially, the bending rigidity of QAFS/Fab fall from 513mN to 268mN. Compared with the unfinished fabric, it has less impact on the whiteness and hygroscopicity of QAFS/Fab, AFSS/Fab, CFSS/Fab. The oil repellency of QAFS/Fab, AFSS/Fab, CFSS/Fab have reached B grade. The decontamination effect of water-soluble stains (cola and coffe) is very good and reaches five grade. The decontamination effect of oil-soluble stain (ink and oil) reaches four grade.